Stain-resistant polymers derived from itaconic acid useful as coatings for fibers

ABSTRACT

The present invention relates to non-halogenated hydrocarbon polymeric compositions which impart durable stain resistance to fibrous substrates, particularly nylon containing articles. In addition, it relates to fluorine containing polymeric compositions which impart durable stain resistance to fibrous substrates as above. It relates also to processes in which such substrates are treated so as to impart durable stain resistance to them. It relates further to a manufacturing process for preparing the compositions of the invention.

This application is a division of application Ser. No. 292,862, filedJan. 3, 1989 now U.S. Pat. No. 4,925,906.

BACKGROUND OF THE INVENTION

The patent literature contains significant precedent in the use ofaddition type polymers for use as stain resistant coatings on fibrousmaterials (eg. U.S. Pat. No. 4,695,497). There is not, however,precedent on the use of polymeric materials based largely ondifunctional monomers, eg. itaconic acid, as stain resistant coatingsfor fibrous materials. The compositions of this invention areparticularly advantitious in that they are comprised mainly of lowtoxicity monomers derived from a renewable resource, eg. itaconic acid.

SUMMARY OF INVENTION

The non-fluorine containing polymeric compositions of the presentinvention consist essentially of pure polymers or mixtures of

(1) an addition polymer of a least one monomer having the formula (A)##STR1## where R₁ =H, C5 -C22 alkyl, ##STR2## cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl; m=0-12;

n=0, 1, 2, 3;

X=CH₂, 0 when m>1,

R₂ is chosen from the list above and may or may not be the same as R₁,R₁ and R₂ cannot both be H, and

(2) an addition copolymer of

(a) at least one monomer having the formula described as (A) above,

(b) and may include one or more of the monomers (B) ##STR3## (c) and mayinclude one or more of the monomers of the formula ##STR4## where R₃ isH or CH₃

R₄ is C1-C22 alkyl, ##STR5## cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl; m=0-12;

n=0, 1, 2, 3;

X=CH₂, 0 (when m>1).

The fluorine-containing compositions of the present invention consistessentially of copolymers of

(1) at least one monomer having the formula (A) as above

(2) at least one monomer having the formula

    CF.sub.3 CF.sub.2 (CH.sub.2)X(CH.sub.2)YOC(O)C(R.sub.3)═CH.sub.2 (D)

wherein

X is an integer from 2-18

Y is an integer from 1-15, R₃ is H or CH₃ and

(3) optionally monomer having the formula ##STR6## where R₅ and R₆ maybe H, CF₃ CF₂ (CF₂)X(CH₂)Y, but R₅ and R₆ cannot both be H

wherein

X is an integer from 2-18

Y is an integer from 1-15

For the non-fluorinated hydrocarbon polymers, the preferred polymericcomposition should be as follows: Based upon the total weight of thecomposition, monomer A would constitute between 20 and 100 percent byweight; monomer B would constitute between 0 and 20 percent by weight;monomer C would constitute 0 to 80 percent by weight. More preferably,monomer A would constitute between 70 and 100 weight percent; monomer Bwould constitute between 1 and 10 weight percent and monomer C wouldconstitute between 0 and 30 percent by weight. The total number ofcarboxylic acid end groups should not exceed, on the average, one pertwo monomer units.

The polymeric non-fluorinated hydrocarbon polymers of the presentinvention are useful in imparting durable stain resistance to a widerange of fibrous materials.

For the fluorine containing copolymers, the preferred polymericcomposition should be as follows: based upon the total weight of thecomposition, monomer A would constitute between 20 and 90 percent byweight and monomer D would constitute between 10 and 80 percent byweight and monomer E would constitute between 0 and 80 percent beweight. More preferably, the fluorinated monomers would constitutebetween 40 and 60 weight percent and monomer A would constitute 40 to 60weight percent.

The polymeric fluorinated compositions of the present invention areuseful in imparting stain resistance to fibrous materials as well.

The polymeric compositions of the present invention can be prepared byusing well known polymerization techniques and conditions. They can beprepared using bulk, solution, suspension or emulsion technologies.Preferably, the polymerization process of this invention is run using anemulsion technique. In the most preferred technique, the monomers arecombined with nonionic and anionic surfactants and water to form adispersion. Initiator, preferably 0.5 to 2 mole percent based onmonomers, is then added. The rection is then carried out at atemperature sufficient to promote efficient initiation. In bulkpolymerization, the temperature will be sufficient to keep the monomersin the carried out a a temperature sufficient to promote efficientinitiation. In bulk polymerization, the temperature will be sufficientto keep the monomers in the molten state.

The fluorinated monomers most preferred for the present invention are(meth) acrylate mixtures such that their perfluoroalkyl groups consistmainly of A=2, 4, 6, 8, 10, 12 and B=2. Such materials are described inU.S. Pat. Nos. 3,282,905, 4,147,852 and U.S. Pat. No. 3,645,989.

Conventional free radical initiators such as peroxy compounds and azocompounds may be used. Examples are benzoyl peroxide,2,2'-azo-bis(2-methylpropionitrile), hereinafter AIBM, potassiumpersulfate and the like. Initiator concentration should be between 0.5and 2.0 percent based on the total moles of the monomers. Likewise,conventional chain transfer agents, such as carbon tetrachloride anddodecyl mercaptan in amounts sufficient to control the molecular weight,may be used but are not always necessary.

DETAILED DESCRIPTION OF THE INVENTION

The following tests were used to evaluate the end use properties of thepolymeric compositions of the invention on woven nylon sleeve.

EXAMPLE 1

A 3-liter polymerization vessel charged with bis(cyclohexylmethyl)itaconate (1500g, 4.65mol), AIBN (15.3g, 2 mol %) and toluene (300ml).The flask was flushed with argon and cooled in a dry ice / acetone bath.The contents of the flask were degassed via 4 cycles of argon purgefollowed by evacuation to 0.5 torr. The vessel was then flushed withargon, protected from the atmosphere with an oil bubbler and placed in a60° C. water bath. After two days the vessel was cooled and the viscousmixture was diluted with tetrahydrofuran (2000ml). The polymer solutionwas then slowly added to vigorously stirred methanol (8000ml). Theprecipitated product was then collected via filtration and dried undervacuum at 50° C. White glassy product was obtained in 78% yield. Analiquot of the polymer (0.1g) was disolved in dichloromethane (15ml).White nylon sleeve (5.0g) was dipped in the solution with agitation andsqueezing to ensure penetration of the liquid into the fiber bundles.The sample was then air dried followed by annealing at 105° C. for 15minutes. The samples were stained, washed and rated as described below.The stain repellancy is set forth in Table 1 and wash durability is inTable II.

EXAMPLE 2

A polymerization vessel was charged with bis(docosyl)itaconate (17.5g,0.023mol), bis(octyl)itaconate (8.3g, 0.023mol) and AIBN (0.15g, 2 molpercent). The flask was sealed and degassed under argon via four vacuum/ purge cycles The sealed flask was then placed in a 75° C. bath for 24hours. The molten mass solidified upon cooling. An aliquot of thepolymer was coated onto nylon and treated as above.

EXAMPLE 3

A polymerization vessel was charged with bis(cyclohexylmethyl)itaconate(3.0g, 9.3mmol), DuPont Fluoroacrylate Telomer B (2.0g, 3.8mmol) α, α,α, trifluorotoluene (1.0ml) and AIBN (0.043g, 2 mol%). The flask wasflushed with argon and cooled in a dry ice / acetone bath. The contentsof the flask were degassed via 4 cycles of argon purge followed byevacuation to 0.5 torr. The vessel was then flushed with argon, sealed,and placed in a 60° C. water bath After two days the vessel was cooled,and the viscous mixture was diluted with tetrahydrofuran (100ml). Thepolymer solution was then slowly added to vigorously stirred methanol(800ml). The precipitated product was then collected via filtration anddried under vacuum at 50° C. White glassy product was obtained in 88%yield. An aliquot of the polymer was coated onto nylon and treated asabove.

EXAMPLE 4

A polymerization vessel was charged with bis(cyclohexylmethyl)itaconate(5.0g), Makon 8 surfactant (0.5g) deionized water (9.0ml) and potassiumpersulfate (0.07g). Vigorous stirring was started and thee vessel waspurged with argon for one hour. The sealed vessel was then placed in a50° C. bath with continued stirring. After . 18 hours, the mixture wascooled and treated with methanol (200ml). The white solid product (4.5g,90%) was collected via filtration and dried under vacuum at 50° C. Analiquot of the polymer was coated onto nylon and treated as above.

STAIN TESTING AND WASH DURABILITY Experimental

Coating Procedure: White nylon-6 sleeve (˜5g) was dipped into a CH₂ Cl₂solution (15ml) containing the polymer (0.1g) to be tested. All of thesolution was absorbed and worked into the fiber. The sleeve was then airdried followed by annealing at 105° C. for 15 minutes.

Kool Aid Staining

The nylon swatch to be tested was placed in a large petrie dish.Unsweetened Cherry Kool Aid (30ml) was poured, from a height of twoinches, onto the sleeve. After standing for 5 minutes, the swatch wascleaned with cold tap water and paper towels. The samples were allowedto air dry before stain ranking.

Coffee Staining

The nylon swatch to be tested was placed in a large petrie dish. Coffee,prepared in a drip coffee maker using 100 ml solid grounds (MaxwellHouse ADC) per liter of water, was poured 30 ml, 71° C. from a height of2 inches, onto the sleeve. After standing for 5 minutes, the sample wascleaned and ranked.

Mustard Staining

The nylon swatch to be tested was placed in a large petrie dish. Mustard(2 grams) was dropped onto the fiber from a height of 2 inches. Afterstanding for 5 minutes, the sleeve was cleaned and ranked.

Stain Ranking: The dry sample was sandwiched between a white backgroundand a standard stain scale. Numerical rankings were obtained by matchingthe stain to the scale. A rating of 0 indicates no visible stain and 8represents a severe stain.

Durability Testing: A nylon sleeve coated and annealed as above wassubjected to a standard soap solution at 25° C. (cold wash) or 60° C.(hot wash) for 5 minutes with agitation. The sample was rinsed well withcold tap water, dried by blotting followed by air drying. The dry samplewas then stained and ranked as above.

                                      TABLE 1                                     __________________________________________________________________________    Itaconate Homo and Co-polymer Stain Rankings                                  1A       2A   2D      Kool                                                    R.sub.1 & R.sub.2                                                                      R.sub.1 & R.sub.2                                                                  R.sub.6                                                                             R.sub.5                                                                         Aid ™                                                                           Coffee                                                                            Mustard                                        __________________________________________________________________________    2-pentyl   -- --    --                                                                              3.0  4.0 1.5                                            1-octyl    -- --    --                                                                              3.0  4.5 1.5                                            1-dodecyl                                                                                -- --    --                                                                              5.0  5.0 3.0                                            1-octadecyl                                                                              -- --    --                                                                              2.0  6.5 2.0                                            1-docosyl                                                                                -- --    --                                                                              5.0  3.0 3.0                                            cyclohexyl-                                                                              -- --    --                                                                              6.0  5.0 3.0                                            methyl                                                                        1-docosyl                                                                              2-pentyl                                                                           --    --                                                                              1.5  5.0 1.5                                            1-docosyl                                                                              1-octyl                                                                            --    --                                                                              1.0  2.0 0.5                                            1-octadecyl                                                                            1-octyl                                                                            --    --                                                                              3.0  3.0 1.0                                            cyclohexyl-                                                                            2-pentyl                                                                           --    --                                                                              6.0  4.0 1.0                                            methyl                                                                        1-octadecyl                                                                            1-docosyl                                                                          --    --                                                                              5.0  4.0 1.0                                            cyclohexyl-   perfluoro-                                                                          H 3.0  0.5 0.5                                            methyl        alkyl                                                           untreated sleeve                                                                            --    --                                                                              8.0  8.0 6.0                                            __________________________________________________________________________

The column headings 1A, 2A and 2D refer to the compounds so designatedin the summary of Invention above. In 2D, Y is 2 and X is various valuesfrom 3 to 8. The perfluoroalkyl precursor is duPont Telomer B acrylate.

                                      TABLE II                                    __________________________________________________________________________    WASH DURABILITY                                                                                     Wash     Kool                                           1A     2A    2D       Con-                                                                              Number                                                                             Aid ™                                       R.sub.1 & R.sub.2                                                                    R.sub.1 & R.sub.2                                                                   R.sub.6                                                                             R.sub.5                                                                          ditions                                                                           washes                                                                             Stain                                          __________________________________________________________________________    Cyclohexyl-                                                                            --  --    -- Cold                                                                              1    7.0                                            methyl                                                                        Cyclohexyl-                                                                            --  --    -- Cold                                                                              2    7.5                                            methyl                                                                        Cyclohexyl-                                                                            --  --    -- Hot 1    3.0                                            methyl                                                                        1-octyl                                                                              1-docosyl                                                                           --    -- Cold                                                                              1    2.0                                            1-octyl                                                                              1-docosyl                                                                           --    -- Cold                                                                              2    3.5                                            1-octyl                                                                              1-docosyl                                                                           --    -- Hot 1    3.0                                            Cyclohexyl-                                                                            --  perfluoro-                                                                          H  Cold                                                                              1    3.0                                            methyl       alkyl                                                            Untreated                                                                              --  --    -- Cold                                                                              1    8.0                                            Sleeve                                                                        Untreated                                                                              --  --    -- Hot 1    7.5                                            Sleeve                                                                        __________________________________________________________________________

We claim:
 1. A stain resistant fiber whose coating comprises copolymersof ( 1) at least one monomer having the formula (A) ##STR7## where R₁ isH, C₅ -C₂₂ alkyl, ##STR8## cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl; m=o-12n=o, 1, 2, 3; X=CH₂, o when m>1, R₂ is chosen fromthe list above and may or may not be the same as R₁, R₁ and R₂ cannotboth be H (2) at least one monomer having the formula (D)CF₃ CF₂(CF₂)XCH₂ YOC(O)C(R₃)═CH₂ wherein X is an integer from 2-18 Y is aninter from 1-15, R₃ is H or CH₃, (3) and may contain a monomer havingthe formula ##STR9## where R₅ and R₆ may be H, CF₃ CF₂ (CF₂)X(CH₂)Y, butR₅ and R₆ cannot be H wherein X is an inter from 2-18 Y is an integerfrom 1-15.
 2. The composition of claim 1 where the fiber is nylon.